DE3721498A1 - COLOR MIXTURES, CONTAINING ISOCHINOL DERIVATIVES, THEIR USE IN PRINTING INKS AND NEW ISOCHINOL DERIVATIVES - Google Patents

Description

The present invention relates to new colorant mixtures containing Isoquinoline azo pigments and isoquinoline azo dyes, their use in Printing inks and new isoquinoline azo dyes.

EP-A-74 048 discloses isoquinoline azo pigments which are particularly useful suitable for use in printing inks.

The color strength or color strength as well as the transparency of these pigments decreases with decreasing crystal size. Therefore, there is interest in to specifically reduce the size of the crystal particles.

However, reducing the crystal size leads to a corresponding one Increase in the viscosity of the ink in which the pigments are included, and to a deterioration in gloss of the thus produced Prints. The practical use thus sets a lower limit for the Crystal size.

The object of the present invention was to create new colorant mixtures To provide, which no longer have the disadvantages mentioned and at which make better use of the color of the isoquinoline azo pigments.

New colorant mixtures have now been found containing Isoquinoline azo pigments of the formula I

in the

X represents chlorine, bromine, C₁-C₄ alkoxy or nitro and
n represents 1, 2 or 3 and the ring A can be substituted

and isoquinoline azo dyes of the formula II  

in the

Y for C₆-C₂₀ alkoxy, optionally by one or more Oxygen atoms is interrupted, and the ring A can be substituted.

All alkyl radicals occurring in the above formulas I and II can be both straight and branched.

X in formula I stands for example for methoxy, ethoxy, propoxy, Isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy.

Y in formula II stands for example for hexyloxy, 2-methylpentyloxy, Heptyloxy, octyloxy, 2-ethylhexyloxy, isooctyloxy, nonyloxy, isononyloxy, Decyloxy, isodecyloxy, undecyloxy, dodecyloxy, tridecyloxy, 3,5,5,7-tetramethylnonyloxy, isotridecyloxy, tetradecyloxy, pentadecyloxy, Hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy (the Designations are isooctyl, isononyl, isodecyl and isotridecyl Trivial names and derive from those obtained after oxo synthesis Alcohols - cf. Ullmann, Encyclopedia of Technical Chemistry, 4. Edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436)), 2-methoxyethoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 3-methoxypropoxy, 2-methoxypropoxy, 2-methoxybutoxy, 2-ethoxybutoxy, 4-methoxybutoxy, 4-ethoxybutoxy, 3,6-dioxahexyloxy, 3,6-dioxaoctyloxy, 3,6-dioxadecyloxy, 3,6,9-trioxadecyloxy, 3,6,9-trioxaundecyloxy or 3,6,9-trioxatridecyloxy.

In the event that the alkyl chain of the radical Y by oxygen atoms is interrupted, those alkyl radicals are preferred which are separated by one or two or three oxygen atoms are interrupted.

In the event that ring A is substituted in formula I and / or II, come as substituents C₁-C₄-alkyl, C₁-C₄-alkoxy, nitro or halogen in Consider. The ring A can be substituted one or more times be.

Isoquinoline azo dyes of the formula II are new. You let yourself go known manner by diazotization of the corresponding Anthranilic acid esters and coupling to isoquinolines, such as those from the EP-A-74 048 are known.  

Colorant mixtures, the isoquinoline azo dyes of the formula II contain, in which Y is C₈-C₁₄-alkoxy, are preferred.

Colorant mixtures which are particularly preferred Contain isoquinoline azo dyes of the formula II, in which Y for 2-ethylhexyl, isononyl, decyl, isodecyl or isotridecyl. As above already stated, it is the isononyl, isodecyl and Isotridecyl compounds around mixtures of isomers.

Isoquinoline azo pigments of the formula I are known from EP-A-74 048.

Preferred colorant mixtures are the isoquinoline azo pigments Contain formula I, which are derived from the diazo component 2-nitroaniline, 2-methoxyaniline, 4-chloro-2-nitroaniline, 4-methoxy-2-nitroaniline or Derive 2,5-dichloroaniline.

The isoquinoline azo pigments of the formula I can also be used as mixtures are available.

The new colorant mixtures contain isoquinoline azo pigments of the formula I. or mixtures thereof and isoquinoline azo dyes of the formula II or Mixtures thereof in a weight ratio of 55:45 to 95: 5, preferably 70:30 to 90: 10.

The favorable quantitative ratio of the long-chain dye of the formula II to the pigment of formula I ultimately depends on that for the Printing ink desired properties and is through simple preliminary tests easy to determine.

The new colorant mixtures can be prepared either by mixing the water-moist press cake of pigment I and dye II or through Dry mixing of pigment I and dye II take place. It is also possible, the respective diazo components of pigment I and dye II diazotize separately and then together on the To couple isoquinoline coupling component.

The colorant mixtures according to the invention are advantageously used for the production of gravure inks, in particular for the production of Gravure inks based on toluene. To do this, they are inserted in the usual way Printing inks incorporated.

The colorant mixtures according to the invention are notable for use in Toluol gravure compared to the known isoquinoline azo pigments of the formula I. in that the prints are glossy, glazed and on natural paper are stronger in color. In addition, the prints beat less with thin paper by. These improved properties are also apparent when storing the Maintain ink so that corrections are not necessary before use.

The following examples are intended to explain the invention in more detail. In them the parts and percentages relate, unless otherwise stated noted on the weight.

Example 1

160 parts of isotridecyl anthranilate were dissolved in 160 parts of glacial acetic acid and 160 parts of ice water are mixed with 150 parts of room 32% hydrochloric acid. To The addition of a further 600 parts of ice water gave 150 parts of 23% strength Sodium nitrite solution added quickly. It was made with 2000 parts of ice water filled up and stirred for about 30 min.

This diazonium salt solution was let into a mixture of 155 parts of Coupling component of the formula

Run in 5000 parts of water and 280 parts of 50% sodium hydroxide solution. It this resulted in a temperature of 10 to 15 ° C and a pH of 8 to 9 a. The mixture was stirred for 30 minutes and the suspension was filtered off with suction, washed neutral with water and sucked the residue as dry as possible.

1020 parts of a press cake were obtained, the dye content of which was 26% amounted to.

500 parts of this water-moist pressed material were at 70 ° C in Vacuum drying cabinet dried. 130 parts of a greenish tinge were obtained yellow dye powder (mp: 168 to 172 ° C).

Example 2

85 parts of the pigment of the formula prepared according to EP-A-74 048

were ground and mixed with 15 parts of the dye from Example 1. A yellow colorant preparation was obtained.  

12 parts of this were used to produce a toluene gravure printing ink Preparation with 138 parts of a commercially available phenol modified Rosin resin solution (approx. 35% in toluene) and 300 parts of steel balls (⌀ 2 to 3 mm) dispersed on a Red Devil for 30 minutes and with toluene adjusted to print viscosity.

The prints made with this gravure ink were translucent, shinier and more colorful than correspondingly produced prints that only contained the pigment known from EP-A-74 048 alone.

Example 3

690 parts of press cake (13%) of a pigment of the formula

were with 10 parts of press cake (14%) of a pigment of the aforementioned Formula (with DK = 2-methoxyaniline) and 30 parts press cake (36%) one Dye of the formula

stirred in 500 parts of water at pH 7 to 8 for about 1 hour at 60 ° C (Die Both pigments were prepared in accordance with EP-A-74 048). After that was suction filtered, washed neutral with water and dried. 100 g were obtained a reddish yellow colorant preparation. She pointed similarly cheap Properties like the preparation prepared in Example 2.

Example 4

19 parts of a pigment of the formula prepared in accordance with EP-A-74 048  

and 6 parts of the dye prepared analogously to Example 1 (but with Anthranilic acid isononyl ester as diazo component) together with 300 Parts of steel balls (⌀ 2 mm), 25 parts of toluene and 100 parts of one commercially available lime resinate (50% in toluene / methylcyclohexane 1: 1) 30 Minutes dispersed on a Red Devil. After separating the balls it was with a mixture of binders (75 parts of the above-mentioned calcium resinate solution and 25 parts of toluene) to a pigment content of 10% and dispersed on the Devil for a further 5 minutes.

The orange printing ink obtained gave glazing strong prints, with a significantly better gloss than with the pigment alone produced prints.

Example 5

40 parts of the pigment of the formula obtained according to EP-A-74 048

were prepared together with 4 parts of a similar to Example 1 Dye (but with anthranilic acid decyl ester as the diazo component) ground and mixed.

An intaglio printing ink thus produced as in Example 2 gave greenish yellow, glossy prints with high glaze.

Example 6 (mixed coupling)

30.5 parts of 4-methyl-2-nitroaniline were in a known manner (EP-A-74 048) diazotized and clarified (solution A).  

6.5 parts of anthranilic acid isotridecyl ester were prepared analogously to Example 1 diazotized and also clarified (solution B).

58 parts of the coupling component from Example 1 were converted into 32 parts Sodium hydroxide solution (50%) and 1000 parts of water dissolved and with ice at + 5 ° C cooled (solution C).

Solution A and solution B were combined and cooled to 0 ° C with ice. Solution C was then run in over the course of 15 minutes, during which a pH of approx. 3.5 and a temperature of + 3 ° C. The Coupling mixture was stirred for 2 hours and at room temperature aspirated. After washing and drying, 90 parts of a reddish tinge were obtained yellow colorant preparation. The printing ink produced with it showed properties similar to those of the preparation obtained in Example 4.

Claims (5)

1. Colorant mixtures containing isoquinoline azo pigments of the formula I. in derX for chlorine, bromine, C₁-C₄ alkoxy or nitro and
n is 1, 2 or 3 and ring A can be substituted and isoquinoline azo dyes of the formula II in derY represents C₆-C₂₀-alkoxy, which is optionally interrupted by one or more oxygen atoms, and the ring A can be substituted. 2. Colorant mixtures according to claim 1, characterized in that Y represents C₈-C₁₄ alkoxy. 3. Colorant mixtures according to claim 1, characterized in that they 55 to 95% by weight of isoquinoline azo pigments of the formula I and 45 to Contain 5 wt .-% of isoquinoline azo dyes of the formula II. 4. isoquinoline azo dyes of the formula II, in which Y is C₆-C₂₀-alkoxy, which is optionally interrupted by one or more oxygen atoms, and the ring A can be substituted. 5. Use of the colorant mixtures according to claim 1 in printing inks.